Antistatic agents for textile materials



United States Patent Ofiice atented Jan. 2, 1958 3,361,718 ANTISTATIC AGENTS Fon TEXTILE TERIALS MA Takehil-ro Fujimoto and Mikishige Murata, Kyoto, Nobuo Obokata, Hirakata, and Shoichi Kita, Qtsu, Japan, assignors to Sanyo Chemical Industry Company, Ltd, Kyoto, Japan No Drawing. Filed May 18, 1964, Ser. No. 368,387 Claims priority, application Japan, Sept. 23, 1963, 38/ 51,152 9 Claims. (Cl. 26049) ABSTRACT OF THE DISCLOSURE 15 The present invention relates to antistatic and antiyellowing agents for textile materials, methods of imparting antistatic and antiyellowing properties to textile materials therewith, and textile materials having both antistatic and antiyellowing properties. More particularly, it relates to an antistatic and antiyellowing agent for textile materials which contains a substantially water-insoluble compound consisting of a high molecular weight part and anionic parts, to a method of imparting antistatic and antiyellowing properties to textile materials by treating the same or covering their surfaces with the said compound, and to textile materials having a surface film containing the said compound.

In the present invention, the term antiyellowing means preventing the textile materials from yellowing due to the absorption or adsorption thereon of a trace of iron in water, and the term substantially Water-insoluble means water-insoluble, or slightly water-soluble or partially water-soluble, i.e. being able to be in the state of aqueous colloidal solution, aqueous dispersion or aqueous emulsion with or withotu emulsifier.

There have been proposed several methods for imparting antistatic properties which are resistant to washing and dry cleaning to textile materials. Out of these methods, the most useful are apparently those described in US. Patents Nos. 2,694,688, 2,723,246, 2,723,256, 2,729,- 577 and 2,741,568, and British Patent No. 819,021. In these methods, textile materials are treated with a cationic high molecular weight compound and, then or simultaneously, with a. certain anionic compound. However, these conventional methods have various drawbacks, for example, the textile materials treated in these manners tend to yellow as they are repeatedly worn and washed, for in the process of washing they absorb or adsorb a trace of iron in water. Furthermore, such textile materials would have too harsh hand. Such antistatic agents or methods of imparting antistatic properties to textile materials as would cause the materials to yellow when repeatedly laundered can not safely be applied to synthetic textile products having wash-and-wear properties, and particularly, to clothes for which a high degree of whiteness is always a prime consideration.

It is therefore an object of the present invention to provide durable antistatic agents for textile materials, par ticularly synthetic fibers such as polyesters, nylons, polyacrylonitriles, acetates, and polyolefins which tend to ac cumulate electrostatic charge, woven and knitted articles made up therefrom, the resulting textile materials treated with said antistatic agents being substantially free from tendencies to yellow due to adsorption of a trace of iron in water as they are subjected to repeated :cycles of wearing and washing.

It is another object of the present invention to provide methods of imparting antistatic and antiyellowing properties to textile materials.

It is a further object of the present invention to provide textile materials having excellent antistatic and antiyellowing properties.

Other objects and features of the present invention will be apparent from the following more detailed description.

We have found that the yellowing tendency due to adsorption of iron in Water of textile materials which have been treated with a cationic high molecular weight compound and, then or simultaneously, with various type of anionic compounds relates to the kind of anionic compounds used, and we have also found that the disadvantages of the conventional methods may be eliminated without adversely affecting the advantages of such methods if a member of the class consisting of certain carefully selected anionic compounds, i.e. anionic compounds each having more than 4 carbon atoms and from 2 to 10 anionic functional groups per molecule, is employed.

In the methods disclosed in the aforementioned US. and British patents, those anionic compounds listed in Table 1 are utilized.

TABLE 1 Anionic compounds which are conventionally employed:

Fatty acid salts Sodium and ammonium laurates Sodium and ammonium myristates Sodium behenate Tallow fatty acid soap sulfates- Sodium octyl sulfate Sodium, potassium, and ammonium dodecyl sulfates Technical sodium dodecyl sulfate Sodium tetradecyl sulfate Sodium hexadecyl sulfate Sodium salt of mixed C -C alkenyl sulfates (alcohols derived from sodium reduction of sperm oil) Sodium hexadecenyl sulfate Sodium octadecenyl sulfate Sodium allryl sulfate having 20 carbon atoms N-diet'nyl cyclohexyl ammonium dodecyl sulfate When such organic compounds, e.g. fatty acid salts,

sulfates, phosphates, and sulfonates as respectively have only one anionic functional group per molecule are employed, the treated textile materials tend to adsorb the traces of iron in water, and consequently assume a yellowish cast. A similar drawback is incurred if organic compounds having a great many anionic'functional groups p per molecule, e.g. a high molecular weight copolyrner of styrene and maleic acid, are employed. We have found that this undesirable result can be avoided, according to the invention, by using organic compounds having more than 4 carbon atoms and from 2 to 10 anionic functional groups per molecule.

Thus, the present invention consists in (1) an antistatic and antiyellowing agent for textile materials which contains a substantially water insoluble compound consisting of a high molecular weight part having a number of quaternary nitrogen atoms and anionic parts each having more than 4 carbon atoms and from 2 to 10 anionic functional groups, the cationic part and anionic parts being chemically combined, (2) a method of imparting antistatic and antiyellowing properties to textile materials by treating or covering surfaces of textile materials with the said compound, and (3) textile material having a surface film containing the said compound.

Any of the compounds consisting of the high molecular weight part having a number of quaternary nitrogen atoms and anionic parts each of which hasmore than 4 carbon atoms and from 2 to 10 anionic functional groups, the high molecular part and anionic parts being in the chemically combined form, may be used as the antistatic and antiyellowing compounds of the present invention. Typical and preferred compounds are those consisting of a high molecular weight part having a number of radicals selected from the class consisting of radicals having the following general Formula I or II, and anionic parts each having more than 4 carbon atoms and from 2 to 10 anionic functional groups selected from the class consisting of COO, SO OSO OPO OPO M, ==O PO PO;, and PO M, wherein M is a member of the class consisting of hydrogen, metal atoms, ammonium radical and organic ammonium radicals:

wherein R and R are members of the class consisting of alkyl radicals having from 1 to 12 carbon atoms, alkenyl radicals having from 3 to 12 carbon atoms, hydroxyalkyl radicals having from 2 to 12 carbon atoms and alkoxyalkyl radicals having from 2 to 12 carbon atoms, or R and R represent a single group which forms a heterocyclic ring having 5 to 6 ring members including the N atom and may contain a second hetero atom 'of the class consisting of O, N and S as a ring member, and which may have alkyl side chains having from 1 to 6 carbon atoms, and R is a member of the class consisting of alkyl radicals having from 1 to 18 carbon atoms, alkenyl radicals having from 3 to 18 carbon atoms,'hydroxyalkyl radicals having from 2 to 18 carbon atoms, alkoxyalkyl radicals having from 2 to 18 carbon atoms, aralkyl radicals having from 7 to 20 carbon atoms, phenoxyalkyl radicals having from 7 to 20 carbon atoms and epoxyalkyl radicals containing from 3 to 18 carbon atoms.

B4 (II) wherein R and R are members of the class consisting of hydrogen and alkyl radicals having from 1 to 6 carbon atoms, m and n are integers of 1 to 2, and R is as defined above in general Formula 1.

Among high molecular weight parts having a number of the radicals of the Formula I, those having at least 20% by weight of a structural unit having the following general Formula III are particularly preferable:

from 2 to 4 carbon atoms, alkoxyalkyl radicals having from 2 to 5 carbon atoms, aralkyl radicals having from 7 to 8 carbon atoms and epoxyalkyl radicals having from p 3 to 8 carbon atoms.

These compounds of this invention may be produced in any known manner. For example, they may be pro-' duced by reacting a compound (hereinafter referred to as cationic compound) consisting of a high molecular weight part having a number of the radicals shown by the above mentioned Formulas I, II or III and common counter-anions, e.g. Cl, Br, I, CH OSO C H OSO and N0 with a compound (hereinafter referred'to as anionic compound) consisting of anionic part having more than 4 carbon atoms and from 2 to 10 anionic functional groups selected from the class consisting of COO, -SO OSO OPO OPO M, =O PO PO;, and -PO M wherein M is a member of the class consisting of hydrogen, metal atoms, ammonium radical and organic ammonium radicals and common countercations, e.g. H, Na, K, Ca, NH CH NH z 4 )s 3)4 2 5)4 and The said cationic compound is produced by polymerizing a monomer having an ethylenic unsaturation or a polymerizable double bond and quaternary nitrogen atom (or copolymerizing the same with a suitable copolymerizable monomer), or by polymerizing a monomer having an ethylenic unsaturation or a polymerizable double bond and tertiary nitrogen atom (or copolymerizing the same with a suitable copolymerizable monomer) and then quaternizing the tertiary nitrogen atoms.

Alternatively, the compounds of this invention may be produced by reacting a monomer having an ethylenic unsaturation or a polymerizable double bond and quaternary nitrogen atom with the anionic compounds, and polymerizing the resulting monomer (or copolymerizing the same with a suitable copolymerizable monomer).

In the compound of the present invention, the preferred average molar ratio of the quaternary nitrogen atom and the anionic part is 1:0.3-1:1.

Some of the exemplary cationic compounds useful in producing the antistatic and antiyellowing compounds of the present invention are shown in Table 2.

TABLE 2 Examples of the cationic compounds useful in producing the compounds of the present invention:

Poly beta acryloyloxyethyltrimethyl ammonium methylsulfate Poly beta acryloyloxyethylemethyldiethyl ammonium ethylsulfate Poly beta methacryloyloxyethyldiethylmethyl ammonium methylsulfate Poly beta methacryloyloxyethyltrimethyl ammonium chloride Poly-beta-methacryloyloxyethyldiethylallyl ammonium chloride Poly beta methacryloyloxyethyldimethylhydroxyethyl ammonium chloride Poly beta methacryloyloxyethyldiethymethoxymethyl ammonium chloride Poly beta acryloyloxyethyldiethylbenzyl ammonium chloride Poly beta acryloyloxyethyldimethylglycidyl ammonium chloride Poly beta acryloyloxyethyldimethylphenoxyethyl ammonium chloride Poly beta vinyloxyethyldiethylmethyl ammoniummethylsulfate Poly beta vinyloxyethyltrimethyl ammonium chloride Poly beta vinyloxyethyldimethylmethoxymethyl ammonium chloride Poly beta acrylamidoethyldiethylmethyl ammonium methylsuifate Poly beta acrylamidoethyldiethylglycidyl ammonium chloride Poly acrylamidopropyldimethylallyl ammonium chloride Poly acrylamidopropyldiethylbutoxymethyl ammonium chloride Polymer obtained by quaternarization of acrylamidoethyldiethylamine with methylol chloroacetamide Poly acrylamidopropylmethyl morpholinium chloride Poly acrylamidoethylbutoxymethyl morphorlinium chloride Poly beta methacrylamidoethylmethyl piperidinium methylsulfate Poly beta vinyloxyethylallyl pipenndinium chloride Poly beta vinyloxyethylmethyl piperidinium chloride Poly N methyl 2 vinyl pyridinium methylsulfate Poly N ethyl 4 vinyl pyridinium chloride Poly N methyl 4 methyl 2 vinyl pyridinium methylsulfate 6 Copolymer of beta methacryloyloxyethyldiethylmethyl ammonium methylsulfate and vinyl acetate Copolymer of beta acrylamidoethyldiethylmethoxymethyl ammonium chloride and acrylamide 5 Copolymer of beta vinyloxyethyldiethylmethyl ammonium chloride and methyl methacrylate.

Some of the exemplary anionic compounds useful in producing the antistatic and antiyellowing compounds of the present invention are those each of which has more than 4 carbon atoms and from 2 to anionic functional groups selected from the class consisting of COO, SO OSO OPO OPO M, -=O PO PO;;, and -PO M, wherein M is a member of the class consisting of hydrogen, metal atoms, ammonium radical and organic ammonium radicals. Among these compounds, those having a molecular weight between 100 and 2000 and from 2 to 6 anionic functional groups per molecule yield particularly satisfactory results in many instances.

Typical and preferred examples of the said anionic compounds are shown in Table 3.

TABLE 3 Polycarboxylic acids Pimelic ac-id Suberic acid Azelaic acid Sebacic acid Itaconic acid Nonylsuccinic acid Nonenylsuccinic acid Dodecylsuccinic acid Dodecenylsuccinic acid Octadecenylsuccinic acid Cyclohexanedicarboxylic acid Isophthalic acid Terephthalic acid Tetrahydrophthalic acid Tricarbarylic acid Trimellitic acid Pyrromellitic acid Polysulfonic acids Benzenedisulfonic acid Butylnaphthalenedisulfonic acid Methylnaphthalenedisulfom'c acid Nonyldiphenyletherd-isulfonic acid Dodecyldiphenyletherdisulfonic acid Diphenyletherdisulfonic acid Phenylphenolsulfonic acid Formalin condensate of naphthalenesulfonic acid Formalin condensate of phenylphenolsulfonic acid Formalin condensate of phenolsulfonic acid Polysulfates Pentaerythritol-ethyleneoxide and propylene-oxide adduct polysulfate (acidic) Ethyleneglycol-propyleneoxide adduct disulfate (acidic) Polybutyleneglycoldisulfate (acidic) Polyphosphates Glycerine-propyleneoxide adduct triphosphate (acidic) Ethyleneglycol-propyleneoxide adduct diphosphate (acidic) Polyphosphonic acids Diphenyletherdiphosphonic acid 70 Compounds having carboxylic and other acid groups Sulfate of oleic acid (acidic) Sulfate of dioxystearic acid (acidic) Sulfonate of monoesterified maleic acid (acidic) a-Sulfonated fatty acid (acidic) Ricinoleic acid phosphate (acidic) 'alkyltrialkyl ammonium compounds, e.g. methacrylamidoethyldiethylmethyl ammonium methylsulfate; vinyloxyalkyltrialkyl ammonium compounds, e.g. vinyloxyethyltrirnethyl ammonium chloride; N-vinyloxyalkyl-N-alkyl piperidinium compounds, e.g. N-vinyloxyethyl-N-methyl piperidinium chloride; N vinyl N alkyl imidazolinium compounds, e.g. N-vinyl-N-methyl imidazolinium methylsulfate; N-alkyl-vinyl pyrid-inium compounds, e.g. N- methyl-2-vinyl pyridinium methylsulfate; and a mixture of two or more of these monomers.

Typical examples of the monomer having an ethylenic unsaturation or a polymerizable double bond and tertiary nitrogen atom include dialkylaminoalkyl acrylates, e.g. beta-diethylaminoethyl acrylate; dialkylaminoalkyl alk acrylates, e.g. beta-diethylaminoethyl methacrylate and beta-dimethylaminoethyl methacrylate; and vinyl pyridines, e.g. 4-vinyl pyridine, Z-methyl-S-vinyl pyridine and 2,4-diethyl-5-vinyl pyridine.

The copolymerizable monomers are those having at least one ethylenic unsaturation or polymerizable double bond, and may be exemplified by olefins, e.g. ethylene, propylene and butylene; acrylic compounds, e.g. acrylonitrile, acrylic acid and methyl acrylate; alkacrylic compounds, e.g. methacrylamide and methyl methacrylate; vinylidene compounds, e.g. vinylidene chloride; vinyl compounds, e.g. vinyl halides, vinyl acetate, styrene, methylvinyl ketones, vinylpyridines and vinyl isobutyl ethers; and dienes, e.g. butadiene and 2-chlorobutadiene.

The amount of copolymerizable monomer may vary from 0% to 80% by weight based on the monomers used. The choice depends on the economics and the desired physical properties of the polymer. If a copolymerizable monomer is used, its preferred amount is from 1% to 50% by weight.

The degree of polymerization of the cationic compound in the above-mentioned methods is greater than (containing at least by weight of the monomer having a polymerizable double bond and quaternary nitrogen atom), but the degree is not directly related to the desired antistatic and antiyellowing properties. Thus, within the range of degree of polymerization obtainable by conventional methods, the resulting compound shows satisfactory properties and can be easily applied to textile materials, e.g. poly-beta-methacryloyloxyethyldiethylmethyl ammonium methylsulfate having a viscosity of 2,000- 100,000 c.p.s. in the form of aqueous solution at room temperature gives good results.

Methods of imparting antistatic and antiyellowing properties to textile materials according to the present invention may be classified into the following two major methods.

(1) Textile materials are treated with an emulsion or a solution containing the compound of the present invendrocarbons, and aromatic hydrocarbons, or any suitable mixtures of two or more thereof to form an antistatic and antiyellowing agent of this invention. If required, it is possible to add some emulsifiers such as nonionic surface active agents, textile softeners, optical brighteners, finishing resins, etc. The resulting solution or emulsion may be applied to textile materials by suitable methods, e.g. coat-I ing, padding, dipping, and spraying.

The second method may be further divided into two as follows:

(a) Textile materials are treated first with the cationic compound and then with the anionic compound (this procedure may be reversed) to form the compound of this invention in situ on the textile materials.

(b) Textile materials are immersed in a bath containing the cationic compound and then the anionic compound is added to the bath (this procedure may be reversed) to form the compound of this invention in situ on the textile materials.

According to the method (2-a), textile materials are treated first with a solution or an emulsion containing the cationic compound by way of, for example, dipping, padding or spraying, and then with a solution containing the anionic compound. The antistatic compound of the present invention is formed on the textile materials. It is the same as in the first method that various additives can be incorporated in the bath. a

The method (2-b) comprises dipping textile materials in a bath containing the cationic compound and, while this bath is constantly stirred, adding a solution containing the anionic compound to the said bath to form the antistatic and antiyellowing compound of the present invention on the textile materials. This method is characterized in that textile materials can be caused to absorb the effective ingredients in the bath more economically, and in that textile materials such as knitted goods, rugs and threads are imparted antistatic and antiyellowing properties without squeezing them too tightly. Just as in the before-mentioned methods, it is possible to incorporate various additives in the bath.

While, in methods (2-a) and (Z-b), the proportion of the cationic compound and the anionic compound is not so critical, it will prove beneficial to use about one or more equivalent amount of anionic compounds.

In any of the said methods, the concentration of the solution may vary over a Wide range, but 0.1% to 5% (by weight) solution is particularly preferred. The treating temperatureis not critical, no substantialdifference in effect being observed if the treatment is conducted at high or low temperature. Textile materials are usually treated with an aqueous bath at a temperature from room temperature to about 50 C.

The antistatic and antiyellowing agent of the present invention may be advantageously applied to textile materials such as fibers, filaments, yarns, knitted and woven fabrics, and the like, made up wholly or partially, from nylons, polyacrylonitriles, polyesters, polyolefins, Wool, etc. which are apt to be electrically charged and tend to yellow upon adsorption of the traces of iron in water as washing is repeated.

The amount of the antistatic and antiyellowing compound of the present invention to be deposited on the textile materials may vary over a wide range. Generally, 0.1 to 5 percent by Weight of the compound of this invention based on the textile materials would yield a satisfactory result.

The antistatic and antiyellowing agent according to the present invention imparts good durable antistatic prop erty to textile materials, and much better antiyellowing property to textile materials than conventional agents.

The effects of the antistatic and antiyellowing com- TABLE 4 The results of a test in which plain-woven nylon cloths were treated with poly-beta-metacryloyloxyethyldiethylmethyl compounds with their anionic parts varied.

Antistatic properties (electric whiteness (reflecresistauces in ohm) tances in percent) N o. Anionic parts J'ust Washed Dry- Before After treated 5 times cleaned iron-test iron-test 5 times 3X10 5 6X10 4X10 9 87. 78. 3X10 7 6X10 5 5X10 7 87. 0 78. 4. 7X10 7 8X10 5 8X10 7 87. 0 78. 1 3X10 7 5X10 5 6X10 7 87. 0 77. 3 2X10 7 6X10 9 1X10 8 86. 4 75. 3

2X10 7 8 X 8 2X10 5 87. 0 77. 2 2X10 7 4X10 5 3X10 7 87. 0 85. 4 3X10 7 4X10 8 4X10 7 87. 0 80.0 6X10 7 5X10 8 4X10 1 87. 0 85.4 N onyldiphenylether d fonate 3X10 7 2X10 3X10 7 87. 0 86. 0 Diphenylether diphosphonate 2X10 8 3X10 7 3X10 7 86.9 85.4 Sorbitol-propyleneoxide adduct phosphate 2X10 7 7X10 8 3X10 7 87. 0 85. 2 Polybutylene-glycoldisulfate 3X10 1 7X10 5 5X10 1 87.0 85.3 14 Control. 1X10 1X10 11 87. 0 80. 3

Notes:

Treatment-Each test cloth was immersed in a 1% aqueous bath of the compound at 40 C., squeezed to 50% pick-up, and dried.

Test 0 antistatic pr0perties.Each test cloth was conditioned so as to be C. and 65% RH (Relative Humidity), and the electric resistance in ohm between both sides of the cloth was measured with a supermegaohmmeter.

Washing tesA-Each test cloth was washed with a 0.2% aqueous solution of a household synthetic detergent at C. for 10 minutes in liquor ratio of times with a Launder-Ometer, rinsed, and dried.

Dry-cleaning test.Each test cloth was washed in petroleumebased dry-cleaning solvent at room temperature (25 C.) for 10 minutes in liquor ratio of 50 times with a Launder-Ometer, rinsed with rfresh solvent, and dried.

Iron adsorption test.A solution of ferric hydroxide (pH 7) containing 240 ppm. of iron was prepared from iron alum and sodium hydroxide. Each test cloth was 40 treated with this solution at 40 C. for minutes in liquor ratio of times, followed by rinsing with water and drying. The reflectance of each test cloth in percent before and after the above treatment was measured at 450 mu Wave length by means or" a photo electric colorim- 45 eter compared with the reflectance of MgO as 100%.

These values, which will be referred to as whiteness, were compared with each other.

TABLE 5 The results of series of tests in which plain-woven nylon cloths were treated with polyacrylamidopropyltrimethyl ammonium compounds with their anionic parts varied. (The procedures of treatment and the methods of measurement are the same as in Table 4.)

Antistatic properties (electric Whiteness (reflecresistauces in ohm) tances in percent) No. Anionic parts .Tust Washed Dry- Before After treated 5 times cleaned iron-test iron-test 5 times 5X10 7X10 1X10" 87.0 77.2 3x10 6x10 5Xl0 87.0 78.2 2X10 6X10 2x10 87. 0 76. 4 Lauryl phosphate 1Xl0 6X10 8x10 86. 9 76. 7 Polyacrylate (degree of polymerization, 3,000)- 4x10 9X10 2X10" 87. 0 77.2 N onylsueeinate 4x10 7X10 5x10 87. 0 84. 7 Dodecenylsuccinate..- 3x10 4x10 4x10 87. 0 86. 5

Nonyldiphenylether disulfonate 2x10 5X10 5x10 86. 8 85.8 Diphenylether disulionate.. 1x10 6X 10 4x10 87. 0 86. 0 Control 1X10 1X10 87. 0 80. 3

TABLE 6 the same as in Table 4.)

Antistatic properties (electric whiteness (reflecresistanees in ohm) tances in percent) No. Anionic parts Just Washed Dry- Beiore After treated 5 times cleaned iron test iron-test 5 times Methylsulfate 8X10 4X10 4X10 86. 4 71. 5 Tallow fatty acid- 5x10 3x10 7 X10 86. 4 72. l Octadecenylsultate. 5X10 4X 10 7 10 86. 4 70. 3 Lauryl phosphate 2X10 4X10" 7 X10 86. 4 70. 8 Dodecylbeuzene sultonate 4X10 3X10 6X10 86. 3 70.8 Nonylsuccinate 5X10 4X10 6X10 86. 3 84. 5 Dodecenylsuccinate 2X10 3x10 4X10 86. 4 86. Diphenylether-diphosphonate- 2X10 3X10 x10 86. 4 84. 4 Nonyldiphenylether disulionate 4X10 4X10 6X10 86.3 83. 4 Control. 1X10 1X10 87.0 80. 3

TABLE 7 of measurement are the same as in Table 4.)

Antistatic properties (electric Whiteness (reflecresistances in o tances in percent) No. Anionic parts Just Washed Dry- Before After treated 6 times cleaned iron-test iron-test 5 times Methylsulfate 4X10 3X10 6X10 87. 3 79. 4 Tallow fatty acid 7X10 5X10 7X10 87. 4 79. 6 0ctadecenylsulfate 6X10 5X10 7X10 87. 3 78. 2 Lauryl phosphate 3X10 6X10 5X10 87. 3 77. 6 Dodeeylbenzeue sulfonate 7 X 5X10 7X10 87 2 79. 4 N onylsuccinate 5X10 7Xl0 6X10 87. 3 85. 2 Dodecenylsuccinate 4x10 5X10 5X10 87. 3 86. 8 Dodecyldiphenylether dlsulfonate 6X10 5X 10 7X10 87. 3 86. 4 Diphenylether diphosphonate 4X10 5X10 6X10 87. 3 86. O Sorbitol-propyleneoxide adduct phosphate 5X10 7X10 7 X10 87. 2 85. 1 Con 1X10 1X10 87. O 80. 3

It will be apparent from the Tables 4 to 7 that ii the high molecular weight part remains the same, there are no substantial difierences in both antistatic properties and resistance to washing and dry-cleaning among the cloths treated with the conventional antistatic compounds and the antistatic and antiyellowing compounds of the present invention. However, when comparisons are made with respect to the tendencies of textile materials to yellow upon adsorption of iron, there are marked diiferences in the degree of yellowing. Thus, the cloths treated with the compounds of the present invention, e.g. Nos. 7-13 of the Table 4, Nos. 6'9 of the Table 5, Nos. 6-9 of the Table 6, and Nos. 6-10 of the Table 7, adsorb much less of the iron in water than the cloths treated with the conventional antistatic compounds, e g. Nos. 1-6 of the Table 4, Nos. 1-5 of the Table 5, Nos. 1-5 of the Table 6, and Nos. 1-5 of the Table 7.

Stated diiierently, the effect of the treatment on reduced adsorption of iron is attainable when the high molecular weight part is combined with anionic parts each having more than 4 carbon atoms and from 2 to 10 anionic functional groups, and no such effect can be expected when anionic parts each having only one anionic functional group is used. Conversely, it is likewise not possible to attain the satisfactory eifect when the anionic part has an excessively great number of anionic functional groups, such as sodium polyacrylate (degree of polymerization: 3000; refer to No. 6 of the Table 4 and No. 5 of the Table 5) The textile materials treated with the antistatic and antiyellowing compound of the present invention are less adsorptive of iron and less liable to yellow, even when compared with the controls which have not been treated.

The present invention will be further understood by the following examples, in which parts are by weight, although the scope of the present invention is by no means limited thereto.

Example 1 To 50 parts of a 30%. aqueous solution of poly-betamethacryloyloxyethyldiethyl methyl ammonium methylsulfate (30,000 cps.) was gradually added at room temperature and with stirring a solution prepared by blending 27.3 parts of disodiurn nonylsuccinate, 7 parts of polypropyleneglycol (molecular weight 300) and 15.7 parts of water and heating the resulting mixture to about 50 C., to obtain a White paste (1) which could be readily dispersed in water. Textile materials were immersed in a 3% aqueous emulsion of (I) at room temperature for 5 to 10 minutes, then squeezed and dried. I

The test results are summarized in Tables 8' and 9. From the tables, it is concluded that textile materials treated with (I) have excellent durable antistatic and better antiyellowing properties than those of the corresponding control and those treated with the conventional agent (II), which contains the same ingredients as (I) except that nonylsuccinate is replaced by a conventional anionic group, i.e., octadecnylsulfate.

TABLE 8 The results of a test on the antistatic properties. (The test procedure is the same as in Table 4.)

Plain-woven Plain-woven Polyester-cotton nylon cloth (:2) polyester cloth ($2) broadcloth (52) Agents Just Washed Just Washed Just Washed treated 5 times treated 5 times treated 5 times (I) The present invention. 2X10 7 2X10 B 3X10 1 2X10 B 1X10 5 5X10 1 (II) ConventionaL 3X10 7 5X10 5 5X10 7 7X10 5 1X10 6 5X10 7 Control (none) 1X10 1X10" 3X10 5 TABLE 9 The results 01 a test on the antiyellowing properties. (The test procedure is the same as in Table 4.)

Plain-woven Plain-woven Polyester nylon cloth polyester cotton broadcloth (percent) cloth (percent) (percent) Agents Before After Before After Before After ironironironironironirontest test test test test test (I) The present invention 87.0 85 .4 84.6 83.7 88.3 84.0 (II) Conventional 87.0 77 .3 84.6 75.3 88 .2 62 .4 Control (none) 87.0 80.3 84 .5 81 .5 88.5 77.8

Example 2 Parts A white paste (III) which could be readily dispersed 5 g g i g in water prepared from the following compounds 20- ISO to pen am 1 1 cording to Example 1, was used to treat textile materials W z by the procedure of Example 1. n

Parts In Tables 10 and 11 are summarized the effects, in aqueous solution of poly-beta-methacryloyloxy- 4 comparison, of (III), the corresponding control and the ethyldiethylmethyl ammonium methylsulfate (30,-

conventional agent (IV) which was prepared in the same manner as for (III) except that a conventional anionic group, i.e. octylsulfate, was used instead of dodecenyl- 000 c.p.s.) aqueous solution of monosodium dodecenylsuccinate. 33 succinate.

TABLE 10 The results of a test on the antistatic properties. (The test procedure is the same as in Table 4.)

Plain-woven nylon Plain-woven poly- Plain-woven polycloth (:2) ester cloth (9) proplyene cloth (9) Agents Just Washed J'ust Washed Just Washed treated 5times treated 5 times treated 5 times (III) The present invention 3x10 4Xl0 2x10 3X10 2X10 2x10 (IV) Convent1ona1 7x10 8X10 4x10 6X10 2X10 3X10 Control (none) 1X10 1X10 1X10 TABLE 11 The results of a test on the antiyellowing properties. (The test procedure is the same as in Table 4.)

Plain-woven nylon Plain-woven poly- Plain-woven polycloth (percent) ester cloth propylene cloth (percent) (percent) Agents Before After Before After Before After iron-test iron-test iron-test iron-test iron-test iron-test (III) The present invention 87.0 86.0 84.6 84.1 78.3 76.2 (IV) Conventional. 87.0 78.1 84.5 74.5 78.2 68.1 Control (none) 87.0 87.3 84.5 81 .5 78 .4 72.3

Example 3 50% aqueous solution of disodium butylnaphthalene disulfonate 38. Liquid hydrocarbon 2-methyl-2,4-pentanediol Water 1.

These treated cloths showed satisfactory antistatic and better antiyellowing properties than those of the control and the same cloths treated with conventional agent (VI) which contains the same ingredients as (V) except that butylnaphthalene disulfonate is replaced with a conventional anionic group, i.e., petroleumsulfonate.

Example 4 In a 3% aqueous solution of poly-N-methyl-2-vinylpyridinium methylsulfate (20,000 c.p.s.) were immersed plain-Woven nylon cloths at room temperature for minutes, squeezed and dried. Then, the cloth was further immersed in a 3% aqueous solution of sodium pyrromellitate at 40 C. for 10 minutes to form the antistatic and antiyellowing compound of the present invention thereon, rinsed and dried. When compared with the control (nontreated), and the cloth treated by the conventional method using poly-N-methyl-2-vinylpyridinium methylsuliate and a conventional anionic compound, i.e., sodium octadecenylsulfate, instead of sodium pyrromellitate, the cloth treated by the method of the present invention showed much better antiyellowing properties.

Example 5 When polyester cloths were treated by the procedure of Example 4 using poly-acrylamidopropylbutoxymethyl morpholinium chloride (15,000 c.p.s.) and sodium salt of sorbitol-propyleneoxide' (12 moles) adduct phosphate, good results similar to Example 4 were obtained on the antistatic and antiyellowing test.

Example 6 When polyester-wool blended cloths were treated by the procedure of Example 4 using poly-N-vinyl-N-methyl imidazolinium methylsulfate (20,000 c.p.s.) and sodium salt of alpha-sulfonated stearic acid, good results similar OOUI' IN 16' to Example 4 were obtained on the antistatic and antiyellowing test.

Example 7 A polyester cloth was treated by the procedure of Example 4 using a copolymer of 70% by weight of betamethacryloyloxyethyldiethylmethyl ammonium methylsulfate and 30% by weight of methyl methacrylate (35,000 c.p.s.) and sodium nonyl-diphenylether disulfonate. The

antistatic and antiyellowing roperties of the cloth were greatly improved.

Example 8 A polyester-cotton blended cloth was treated by the procedure of Example 4 using a copolymer of 75% by weight of N-methyl-2-methyl-5-vinylpyridinium bromide and by weight of acrylamide (45,000 c.p.s.) and disodium butylnaphthalenedisulfonate. The antistatic and antiyellowing properties of the cloth were greatly improved.

' Example 9 A polypropylene cloth was treated by the procedure of Example 4 using poly-beta-vinyloxyethyldiethylmethyl- Example 10 Five parts of a 30% aqueous solution of poly-betamethacryloyloxyethyldiethylmethyl ammonium methylsulfate (25,000 c.p.s.) and 5 parts of a cationic softener (Safanol NTQ made by Sanyo Chemical Industry Company, Kyoto, Japan) were dissolved in water to be 2000 parts, in which 100 parts of eachkind of knitted goods made of synthetic fibers was immersed at 40 C. Then, 300 parts of a 1.5% aqueous solution of disodium dodecenylsuccinate was gradually added to the bath. After the addition of disodium dodecenylsuccinate, the goods were left standing for 30 minutes, rinsed and dried.

The test results are summarized in Tables 12 and 13. It isapparent from the tables that the knitted goods treated in this manner (A) have good antistatic properties resistant to washing, desirably soft handles and better antiyellowing properties than the control goods, the goods treated by a method using the anionic compound known to the prior art, i.e. sodium octylsulfate, instead of disodium dodecenylsuccinate (B), and the goods treated with a 1% aqueous solution of poly-beta-methacryloxyethyldiethylmethyl ammonium methylsulfate alone (C).

TABLE 12 The results of a test on the antistatic properties. (The test procedure is the same as in Table 4.)

Polyester-poly- Polyacry1o- Polyesterm) acrylonitrile nitrile (o) Treating methods Just Washed Just Washed Just Washed treated 5 times treated 5 times treared 5 times The present invention (A) 4X10 7 6X10 8 3X10 7 1X10 8 6X10 7 5X10 H The conventional method using sod um The conventional method using sodium octylsulfate (B) 1X10 8 8X10 1X10 9X10" 1X10 8 2X10 9 The conventional method not using anionic compound (C) 2X10 5 1X10 3X10 8 2X10 2X10 8 2X10 9 ontr 3X10 2X10 2X10 TABLE 13 The results of a test on the antiyellowing properties. (The test procedure is the same as in Table 4.)

Polyester Polyester-poly- Polyacrylouitlile (percent) aerylonitrile (percent) (75/25) (percent) Treating methods Before After Before After Before After ironironironironironirontest test test; test test test The present invention (A) 87.3 87. 84. 1 8'2. 4 79. 4 77. 7 The conventional method using sodium octylsulfate (B) a 87.3 75. 6 84.1 75. 2 79. 3 68. 4 The conventional method not using anionic compound (0) 87. 3 77. 5 84. 2 76. 3 79. 3 68. 8 Control 87. 4 82. 3 84. 3 78. 5 79, 4 71, 0

Example 11 Five parts of a 30% aqueous solution of poly-betamethacryloyloxycthyldiethylmethyl ammonium methylsulfate (25,000 c.p.s.) were dissolved in water to be 2,000 parts of a bath, in which 100 parts of a polyester cloth were immersed at 40 C. Then, while the solution was agitated, 300 parts of a 2% aqueous solution of disodium dodecyl sulfosuccinate was gradually added to the bath. After the addition of the disodium dodecyl sulfosuccinate, the cloth was left standing for 30 minutes, rinsed and dried.

The cloth treated as above showed much better antiyellowing property than the control, the cloth treated by a method using the anionic compound known to the prior art, i.e. sodium lauryl sulfate, instead of disodium dodecyl sulfosuccinate and the cloth treated with a 1% solution of polybeta-methacryloyloxyethyldiethylmethyl ammonium methylsulfate alone at room temperature, and also showed good antistatic properties.

What we claim is:

1. An antistatic and antiyellowing agent for textile materials which comprises a substantially water-insoluble compound consisting of a high molecular weight polymer part having a number of quaternary nitrogen atoms and anionic parts each having more than 4 carbon atoms and from 2 to anionic functional groups.

2. An antistatic and antiyellowing agent for textile materials as described in claim 1, wherein the high molecular weight polymer part has a number of radicals selected from the class consisting of radicals having the following general Formula I or H:

HA (I) wherein R and R are members of the class consisting of alkyl radicals having from 1 to 12 carbon atoms, alkenyl radicals having from 3 to 12 carbon atoms, hydroxyalkyl radicals having from 2 to 12 carbon atoms and alkoxyalkyl radicals having from 2 to 12 carbon atoms, or R and R represent a single group which forms a heterocyclic ring having 5 to 6 ring members including the N atom and R is a member of the class consisting of alkyl radicals having from 1 to 18 carbon atoms, alkenyl radicals having from 3 to 18 carbon atoms, hydroxyalkyl radicals having from 2 to 18 carbon atoms, alkoxyalkyl radicals having from 2 to 18 carbon atoms, aralkyl radicals having from 7 to 20 carbon atoms, phenoxyalkyl radicals having from 7 to 20 carbon atoms and epoxyalkyl radicals having from 3 to 18 carbon wherein R and R are members of the class consisting of hydrogen and alkyl radicals having from 1 to 6 carbon atoms, In and n are integers of l to 2, and R is as defined above in general Formula I.

3. An antistatic and antiyellowing agent for textile materials as described in claim 1 wherein the high molecular weight polymer part has at least 20% by Weight of the radicals having the following general formula:

R (III) wherein R is a member of the class consisting of hydrogen and alkyl radicals having from 1 to 2 carbon atoms, R is an a kylcne radical having from 2 to 4 carbon atoms, R and R are members of the class consisting of alkyl radicals having from 1 to 4 carbon atoms and hydroxyalkyl radicals having from 2 to 4 carbon atoms, and R is a member of the class consisting of alkyl radicals having from 1 to 4 carbon atoms, alkenyl radicals having from 3 to 4 carbon atoms, hydroxyalkyl radicals having from 2 to 4 carbon atoms, alkoxyalkyl radicals having from 2 to 5 carbon atoms, aralkyl radicals having from 7 to 8 carbon atoms and epoxyalkyl radicals having from 3 to 8 carbon atoms.

4. An antistatic and antiyellowing agent for textile materials as described in claim 1, wherein each of the anionic parts has from 2 to 10 anionic functional groups selected from the class consisting of -COO, SO OSO =O POg, OPO3, -PO3 and -PO3M, Whr M is a member of the class consisting of hydrogen, metal atoms, ammonium radical and organic ammonium radicals.

5. An antistatic and antiyellowing agent for textile materials as described in claim 1, wherein the anionic parts are the residues selected from the class consisting of alkyl succinic acid residues of which alkyl has from 9 to 18 carbon atoms, alkenyl succinic acid residues of which alkenyl has from 9 to 18 carbon atoms, alkyldiphenylether disulfonic acid residues of which alkyl has from 3 to 18 carbon atoms, alkyl naphthalene-disulfonic acid residues of Which alkyl has from 3 to 6 carbon atoms, polyalkylnaphthalenedisulfonic acid residues of which alkyls respectively have from 3 to 6 carbon atoms and alkyl sulfosuccinic acid residues of which alkyl has from 8 to 18 carbon atoms.

6. An antistatic and antiyellowing agent for textile materials comprising a substantially water-insoluble compound consisting of high molecular weight polymer part which has a number of radicals selected from the class consisting of radicals having the following general Formula I or ll:

wherein R and R are members of the class consisting of alkyl radicals having from 1 to 12 carbon atoms,

alkenyl radicals having from 3 to 12 carbon atoms, hydroxyalkyl radicals having from 2 to 12 carbon atoms and alkoxyalkyl radicals having from 2 to 12 carbon atoms, or R and R represent a single group which forms a heterocyclic ring having to 6 ring members including the N atom and R; is a member of the class consisting of alkyl radicals having from 1 to 18 carbon atoms, alkenyl radicals having from 3 to 18 carbon atoms, hydroxyalkyl radicals having from 2 to 18 carbon atoms, alkoxyalkyl radicals having from 2 to 18 carbon atoms, aralkyl radicals having from 7 to 20 carbon atoms, phenoxyalkyl radicals having from 7 to 20 carbon atoms and epoxyalkyl radicals having from 3 to 18 carbon atoms;

wherein R and R are members of the class consisting of hydrogen and alkyl radicals having from 1 to 6 carbon atoms, m and n are integers or" 1 to 2, and R is as defined above in general Formula I, and anionic parts which have from 2 to anionic functional groups selected from the class consisting of CO0, -SO OSO OPO M, =O PO -OPO PO and PO M, wherein M is a member of the class consisting of hydrogen, metal atoms, ammonium radical and organic ammonium radicals.

7. An antistatic and antiyellowing agent for textile materials comprising a substantially water-insoluble compound consisting of the high molecular weight polymer part which has at least 20% by weight of the radicals having the following general formula:

wherein R is a member of the class consisting of hydrogen and alkyl radicals having from 1 to 2 carbon atoms, R is an alkylene radical having from 2 to 4 carbon atoms, R and R are members of the class consisting of alkyl radicals having from 1 to 4 carbon atoms and hydroxyalkyl radicals having from 2 to 4 carbon atoms, and R isra member of the class consisting of alkyl radicals having from 1 to 4 carbon atoms, alkenyl radicals having from 3 to 4 carbon atoms, hydroxyalkyl radicals having from 2 to 4 carbon atoms, alkoxyalkyl radicals having from 2 to 5 carbon atoms, aralkyl radicals having from 7 to 8 carbon atoms and epoxyalkyl radicals having from 3 to 8 carbon atoms, and anionic parts which have from 2 to 10 anionic functional groups selected from the class consisting of COO, SO OSO OPO M, =O P9 OPO PO and PO M, where M is a member of the class consisting of hydrogen, metal atoms, ammonium radical andorganic ammonium radicals.

8. An antistatic and antiyellowing agent for textile materials comprising a substantially water-insoluble compound consisting of high molecular weight polymer part droxyalkyl radicals having from 2 to 12 carbon atoms and alkoxyalkyl radicals having from 2 to 12 carbon atoms, or R and R represent a single group which forms a heterocyclic ring having S to 6 ring members includ- 2%) ing the N atom and R is a member of the class consisting of alkyl radicals having from 1 to 18 carbon atoms, alkenyl radicals having from 3 to 18 carbon atoms, hydroxyalkyl radicals having from 2 to 18 carbon atoms, alkoxyalkyl radicals having from 2 to 18 carbon atoms, aralkyl radicals having from 7 to 20 carbon atoms, phenoxyalkyl radicals having from 7 to 20 carbon atoms and epoxyalkyl radicals having from 3 to 18 carbon atoms;

wherein R and R are members of the class consisting of hydrogen and alkyl radicals having from 1 to 6 carbon atoms, In and n are integers of 1 to 2, and R is as defined above in general Formula I, and anionic parts which are the residues selected from the class consisting of alkyl succinic acid residues of which alkyl has from 9 to 18 carbon atoms, alkenyl succinic acid residues of which alkenyl has from 9 to 18 carbon atoms, alkyldiphenylether disulfonic acid residues of which alkyl has from 3 to 18 carbon atoms, alkyl naphthalene-disulfonic acid residues of which alkyl has from 3 to 6 carbon atoms, polyalkylnaphthalenedisulfonic acid residues of which alkyls respectively have from 3 to 6 carbon atoms and alkyl sulfosuccinic acid residues of which alkyl has from 8 to 18 carbon atoms.

9. An antistatic and antiyellowing agent for textile materials comprising a substantially water-insoluble compound consisting of high molecular weight polymer part which has at least 20% by weight of the radicals having the following general formula:

3,, (III) wherein R is a member of the class consisting of hydrogen and alkyl radicals having from 1 to 2 carbon atoms, R is an alkylene radical having from 2 to 4 carbon atoms, R and R are members of the class consisting of alkyl radicals having from 1 to 4 carbon atoms and hydroxyalkyl radicals having from 2 to 4 carbon atoms, and R is a member of the class consisting of alkyl radicals having from 1 to 4 carbon atoms, alkenyl radicals having from 3 to 4 carbon atoms, hydroxyalkyl radicals having from 2 to 4 carbon atoms, alkoxyalkyl radicals having from 2 to 5 carbon atoms, aralkyl radicals having from 7 to 8 carbon atoms and epoxyalkyl radicals having from 3 to 8 carbon atoms, and anionic parts which are residues selected from the class consisting of alkyl succinic acid residues of which alkyl has from 9 to 18 carbon atoms, alkenyl succinic acid residues of which alkenyl has from 9 to 18 carbon atoms, alkyldiphenylether disulfonic acid residues of which alkyl has from 3 to 18 carbon atoms, alkyl naphthalene-disulfonic acid residues of which alkyl has from 3 to 6 carbon atoms, polyalkylnaphthalenedi- V sulfonic acid residues of which alkyls respectively have from 3 to'6 carbon atoms and alkyl sulfosuccinic acid residues of which alkyl has from 8 to 18 carbon'atoms.

References Cited UNITED STATES PATENTS 2,729,577 1/ 1956 Bacon et al 117-76 2,741,568 4/1956 Hayek 117-1395 FOREIGN PATENTS t s 597,255 5/1960 Canada 260-895 WILLIAM H. SHORT, Primary Examiner.

M. GOLDSTEIN, Assistant Examiner.

(II) V 

